Inhibiting corrosion and scaling of surfaces contacted by sulfur-containing materials

ABSTRACT

A method of treatment for inhibiting sulfur-based corrosion or scaling or for removing scaling from a surface including inhibiting corrosion caused by sulfur-containing materials, reducing corrosion caused by sulfur-containing materials, inhibiting scaling caused by sulfur-containing and sulfur-containing materials in gas, liquid or solid phase or any combination of multiple phases of materials, reducing scaling caused by sulfur-containing and sulfur-containing materials, and removing scaling caused by sulfur-containing and sulfur-containing materials. The method involves contacting sulfur-containing materials with a composition containing a turpentine liquid. The method also involves contacting corrodible surfaces or surfaces prone to scaling with a composition containing a turpentine liquid.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 12/742,345, filed Jul. 9, 2010, which is a 35 U.S.C. §371National Phase Entry Application from PCT/US2010/026815, filed Mar. 10,2010, and designating the United States, which claims priority to PCTApplication No. PCT/US2009/037112 filed Mar. 13, 2009, which areincorporated herein in their entireties.

FIELD OF THE INVENTION

The present invention relates to the field of inhibiting, reducing,preventing, and removing corrosion and scaling on surfaces contacted bysulfur-containing materials.

BACKGROUND OF THE INVENTION

It is known from laboratory studies and field trials that elementalsulfur reacts aggressively with metals in the presence of water oraqueous solution. The accelerated attack on metals caused by elementalsulfur results in pitting, stress cracking, and mass-loss corrosion.According to the Federal Highway Administration study entitled CorrosionCosts and Preventive Strategies in the United States, the total annualestimated direct cost of corrosion in the U.S. in 1998 was approximately$276 billion (approximately 3.1% of U.S. gross domestic product).

Elemental sulfur is a strong oxidizer, causing corrosion where itattaches to the wet steel surface. Elemental sulfur can occur whenoxygen mixes with H₂S or may be produced naturally. There are few, ifany, commercial inhibitors that effectively protect against corrosioncaused by elemental sulfur.

The trend to use more ImAg (immersion silver) surface finish and shyaway from SnPb HASL (Stannum Lead AntiHot Air Solder Leveling) onelectronic products has resulted in corrosion failure occurrences whenthese products are exposed to high sulfur environments under elevatedhumidity. The resulting creep corrosion constituent is primarily Cu₂Swhich is produced by galvanic driven attack of the copper beneath theedge of the soldermask. Electronic hardware manufacturers areexperiencing, or will soon experience product reliability problems dueto sulfur corrosion at tire burning factories, paper mills, fertilizerplants, and polluted locations in developing countries. This newunexpected failure mechanism demands a controlled process by whichproducts can be qualified to ensure they will not fail in theseapplications.

Prior methods to combat corrosion have included protective organiccoatings, cement, sacrificial anodes, various inhibitors cathodicprotection, and spray-coating corrosion-susceptible surfaces withcorrosion-resistant metals. These methods have been variably effectiveat reducing corrosion rates and come with variable costs and safetyconsiderations. For example, imidazoline-based inhibitors have beenshown to be ineffective in controlling the accelerated localized attackcaused by elemental sulfur while chromate and hydrazine are effectivefor inhibiting corrosion but are carcinogenic.

The inhibition of corrosion on corrodible surfaces in contact withsulfur-containing materials, in solid, semi-solid, liquid, or vapor formhas proven to be extremely challenging. The difficulty can in part beattributed to the fact that these materials contain elemental sulfur,sulfur compounds, and other corrosive elements such as salts, acids, andcorrosive gases which contact corrodible surfaces that give upelectrons, becoming themselves positively charged ions in anelectrochemical reaction. When concentrated locally, this reaction formsa pit or a crack, but may also extend across a wide area to producegeneral corrosion.

Chemical and biological origins are considered to be involved in thecorrosion-causing sulfur reactions. The production of sulfur from thechemical origin is governed by the oxidation-reduction potential and pH,while bacteria, such as sulfur bacteria, participate in the formation ofsulfur from biological origin.

It is widely recognized that microorganisms attach to, form films on,and influence corrosion on surfaces, especially in aqueous environments.Microorganisms causing sulfur-based corrosion include Halothiobacillusneapolitanus, Thiobacillus ferroxidans Acidothiobacillus thiooxidans,Ferrobacillus ferrooxidans, Thiobacillus thiooxidans, Thiobacillusthioparus, Thiobacillus concretivorus, Desulfovibrio andDesulfotomaculum, Sphaerotilus, Gallionella, Leptothrix, Crenothrix,Clonothrix, and Siderocapsa. The microorganisms change theelectrochemical conditions at the surface which may induce localizedcorrosion and change the rate of general corrosion. Some microorganismsreduce sulfate and produce hydrogen sulfide or oxidize H₂S gas to solidsulfur, which can lead to corrosion. Some bacteria produce acids andother corrosive compounds on the surfaces leading to even furthercorrosion. In addition to metal surfaces, microbial corrosion can alsoapply to plastics, concrete, and many other materials. The use ofsurfactants to suppress sulfur bacteria have proven ineffective forlonger periods of time, requiring service within a year of use (Kudo andYuno, Proceedings World Geothermal Congress, 2000).

Formation of scale caused by sulfur or sulfur compounds or fromcorrosion products adhering to the inner surfaces of pipes serves todecrease ability to transfer heat and to increase the pressure drop forflowing fluids. Also, in the presence of other impurities such as ionsof calcium and magnesium in a liquid, e.g., water, gives rise to theformation of scale or voluminous precipitate, thus fouling the surfaces.Scale is an assemblage of precipitates that adhere to surfaces alongwater paths. Accumulated solid layers of impermeable scale can linepipes and tubes, sometimes completely blocking flow. Metal sulfates,e.g., barium and calcium sulfates, form the most persistent scale, whichoften requires shutdown of operations for mechanical removal from themetal walls of pipes, boilers, refinery equipment, production tubing,tanks, valves, etc. In boilers, scale results in reduced heattransmission, higher fuel usage, pipe blockage, and local overheatingwhich can damage the boilers. In industrial operations, scale buildupreduces output, puts pressure on pumps, turbines and propellers, andengines, and eventually requires systemic shutdown for scale removal.Thus, in addition to direct removal costs, the indirect costs of scalingare enormous in terms of equipment damage, reduced efficiency, anddeterred production. Thus, it is preferable to prevent or reduce scalingas much as possible.

Chemical treatment is often the first approach in attempts to inhibit,reduce, or remove scale. It is more advantageous when conventionalmechanical methods are ineffective or expensive to deploy. Priorchemical techniques include contacting the substrate with alkalinesalts, acids, inhibitors such as phosphate compounds, chelatingsolutions, and dispersing agents. Such methods tend to often beineffective and sometimes dangerous or impractical. Often, not enoughscale is removed or inhibited or the chemicals are not compatible withthe systems requiring treatment. Hydrochloric acid is often the firstchoice for scale treatment, but the acid reaction produces by-productswhich are excellent initiators for reformation of scale deposits.Further, in acid descaling, the system must be shut down, drained, acidcleaned, rinsed, drained and retreated. Ethylenediamenetetraacetic acid(EDTA), a chelator, is also commonly used to stoichiometricallysequester metal ions; however, EDTA is slower than hydrochloric acid andstoichiometric treatments require significant concentrations to preventscale formation. Because of the disadvantages of chemical treatments,they have sometimes been abandoned in favor of, or combined with,mechanical techniques to remove or reduce scaling.

Earlier mechanical techniques for scale removal included explosives torattle and break off scale, but often damaged the substrate and did noteffectively remove scale. Modern mechanical techniques include shotblasting, abrasive blasting, water jetting, pressurized air blasting,grinding, milling, impact hammering, and shock waves. These toolsrequire full access to the substrate surfaces plagued by scaling and areseldom effective at completely removing scale to the bare walls.Residual scale on surfaces encourages new growth and makes scaleinhibitor treatments more difficult. Further, such methods, especiallyabrasives, can damage substrate surfaces.

Prior techniques have failed to safely and effectively prevent, reduce,or remove scale and corrosion. A need exists for methods andcompositions to inhibit corrosion of corrodible surfaces by preventingdeposition and/or removing sulfur and other corrosive molecules fromcorrodible surfaces. There is also a need for scale-prevention,scale-reduction, and scale-removal techniques that are more effective,quick, and non-damaging to the substrate and environment.

SUMMARY OF INVENTION

In accordance with one embodiment of the present invention, the presentinvention provides a composition and a method for reducing the rate ofor inhibiting the corrosion of a corrodible surface or material.Surfaces that contact sulfur-containing materials, e.g., transformers,pipes, tanks, pumps, water distribution systems, wastewater and sewagedistribution and treatment equipment, electronics, semiconductors, wood,pulp, paper mills, oil field electronics, flue gas stacks, conductor andtransmission wires, mineral processing, hydrometallurgy operations,metal extraction processes, and metal purification operations are proneto corrosion and/or scaling. By reducing the corrosion and scaling thatafflicts such surfaces, significant cost savings are realized.

In this invention, a composition containing a turpentine liquid is usedto reduce, prevent, or inhibit corrosion from occurring. In oneembodiment corrodible materials are treated with the inventivecomposition. In another embodiment, the composition is added to asulfur-containing material that contacts corrodible surfaces. In yetanother embodiment, corrodible materials are treated with thecomposition and the composition is added to sulfur-containing materialthat contacts corrodible surfaces to provide even further protection.The present invention takes advantage of the very strongphysico-chemical affinity of the turpentine liquid to sulfur and sulfurcompounds.

In another embodiment, descaling, scale inhibition, fouling inhibitionand/or fouling reduction is accomplished by the method of the presentinvention. A composition containing a turpentine liquid is used toreduce, inhibit, and/or remove scaling from surfaces. Scaled surfaces orany surfaces prone to scaling are treated with the composition and/orthe composition is added to materials which contact the surfaces thatare scaled or prone to scaling.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the details of the multiple crevice assembly for thecorrosion tests. FIG. 1A shows the mounted test coupons, and FIG. 1Bshows a close up of the crevice washer.

FIG. 2 shows the test coupons 01 and 02 from the baseline test. FIG. 2Ais the coupons after being chemically cleaned, and FIG. 2B is thecoupons just removed from the baseline solution.

FIG. 3 shows a 65× close up of the baseline test coupon crevice attack.FIG. 3A is the front of test coupon 02, and FIG. 3B is the back of thecoupon 02.

FIG. 4 shows a 65× close up of the inhibitor test coupon crevice attack.FIG. 4A is the front and back of a test coupon treated with inhibitorII, FIG. 4B is the front and back of a test coupon treated withinhibitor I, and FIG. 4C is the front and back of a test coupon treatedwith inhibitor III.

FIG. 5 shows the 14 day baseline coupons upon removal from the test(FIG. 5A) and after cleaning (FIG. 5B). FIG. 5C is a 10× magnificationof the 14 day baseline coupon after testing showing pitting. FIG. 5D isa 10× magnification of the 14 day baseline coupon after testing showingedge attack (circled).

FIG. 6 shows the 14 day inhibitor I coupons upon removal from the test(FIG. 6A) and after cleaning (FIG. 6B). FIGS. 6C and 6D are 10×magnifications of the 14 day baseline coupon after testing showingincipient pitting.

FIG. 7 shows the 14 day inhibitor II coupons upon removal from the test(FIG. 7A) and after cleaning (FIG. 7B). FIGS. 7C and 7D are 10×magnifications of the 14 day baseline coupon after testing showingincipient pitting.

FIG. 8 shows SEM images (100X magnified) of the baseline (FIG. 8A),inhibitor I (FIG. 8B), and inhibitor II (FIG. 8C) corrosion productsafter the 14 day tests with a 3:1 inhibitor to sulfur molar ratio.

FIG. 9 shows the uninhibited test coupons in solid elemental sulfurtests. FIG. 9A shows the test coupon with the sulfur pieces before test;FIG. 9B shows the top; FIG. 9C shows the bottom of the coupon after thetest; and FIG. 9D is a close up of the pitting on the uninhibitedcoupon.

FIG. 10 shows the inhibited test coupons in solid elemental sulfurtests. FIG. 10A shows the test coupon with the sulfur pieces beforeinhibitor I test; and FIG. 10B shows the top and FIG. 100 shows thebottom of the inhibitor I coupon after the test. FIG. 10D shows the testcoupon with the sulfur pieces before inhibitor II test. FIG. 10E showsthe top and FIG. 1OF shows the bottom of the inhibitor II coupon afterthe test.

FIG. 11 shows the sulfur surface adherence and agglomeration tests. FIG.11A shows the test bottle without inhibitor before mixing; FIG. 11 Bshows the test bottle without inhibitor after mixing; FIG. 11C shows thetest bottle with inhibitor I before mixing; FIG. 11 D shows the testbottle with inhibitor I after mixing; FIG. 11 E shows the test bottlewith inhibitor II before mixing; and FIG. 11 F shows the test bottlewith inhibitor II after mixing.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention relates to a readily deployablecomposition for the reduction, prevention, and/or inhibition ofcorrosion on corrodible surfaces that are contacted by sulfur-containingmaterials.

According to one embodiment, a method is provided including the steps ofinhibiting, reducing, or preventing corrosion caused bysulfur-containing materials including those containing elemental sulfurand sulfur compounds. The present invention inhibits all types ofcorrosion including, but not limited to, pitting corrosion, general oruniform corrosion, creep corrosion, stress corrosion, blistering, vaporphase corrosion, crevice corrosion, welding corrosion, and microbialcorrosion. As used herein, sulfur-containing materials include anymaterial that comprises elemental sulfur or sulfur compounds, e.g.,hydrogen sulfide, sulfates, sulfur containing salts and acids, sulfides,disulfides, mercaptans, thiophenes, and benzothiophenes. Examples ofsulfur-containing materials include, but are not limited to,hydrocarbon-containing materials, non-hydrocarbon containing materialsincluding wastewater, groundwater, sewage, pulp water, cooling fluids,gases, and solids. In one embodiment, the hydrocarbon-containingmaterial can be a natural or synthetic hydrocarbon-containing material.Some examples of natural hydrocarbon-containing materials are coal,crude oil, tar, tar sands, oil shale, oil sands, natural gas, petroleumgas, crude bitumen, natural kerogen, natural asphalt, and naturalasphaltene. Natural hydrocarbon-containing materials can be obtainedfrom a natural formation.

Many different surfaces are prone to corrosion, especially metalsurfaces, e.g., steel, aluminum, and copper. However, composite,concrete, plastic, natural polymers, wood, and glass surfaces are alsoprone to corrosion.

In another embodiment, the present invention inhibits, reduces, orprevents corrosion caused by microbial action.

Inhibiting, reducing, or preventing corrosion includes the step ofproviding a sulfur-containing material, contacting the sulfur-containingmaterial with the corrosion-inhibiting composition of the presentinvention prior to or during the sulfur-containing material's contactwith a corrodible surface. In some embodiments, it is preferable for thecorrosion-inhibiting composition to increase the sulfur-containingmaterial's viscosity. The corrosion-inhibiting composition comprises,consists essentially of, or consists of an amount of a turpentineliquid, e.g., terpineol. Turpentine derived from natural sourcesgenerally includes an amount of terpene. In one embodiment, theturpentine liquid includes α-terpineol. Optionally, the corrodiblesurface may be contacted with the corrosion-inhibiting composition ofthe invention prior to, during, or after its contact withsulfur-containing materials. For example, the corrosion-inhibitingcomposition can be used in maritime applications, e.g., on ships, boats,shipping containers, hot chambers of civilian and military navalvessels, port and offshore structures, in aerospace applications, e.g.,on airplane and helicopter frames and components, military and civilianjet plane exhaust components, and jet engine turbine blades, on flue andexhaust stacks, e.g., power plant flue stack walls, gas turbine bladesin power plants, pipes, tanks, boilers, heaters, and electronicsapplications, e.g., on wires, electronics, or semiconductors.

The inventive method and composition also have applications duringtransportation, drilling, downhole operations, exploration, hydrocarbonproduction, storage, handling, or production of hydrocarbon-containingmaterials, for example by pipelines, tankers, casings, fishing tools, ordrill bits, and other surfaces that contact sulfur-containing compounds.

In further embodiments, the turpentine liquid can be separated from thesulfur-containing materials, recycled, and/or reused to maintaincorrosion inhibition.

In yet another embodiment, the corrosion-inhibiting composition can beapplied as a layer over and/or under another protective layer of asurface. For example, to protect corrodible metal surfaces, thecorrosion-inhibiting composition can be applied over or under a chemicaloxidization layer. In another embodiment, the corrosion-inhibitingcomposition can be applied as a layer over and/or under an insulationlayer on a substrate. Examples of insulation layers include, but are notlimited to, oxides, nitrides, and polymers.

The present invention provides a method for significantly reducingcorrosion by the addition of a corrosion-inhibiting composition to asulfur-containing material. When a sulfur-containing material is mixedwith the corrosion-inhibiting composition, the corrosion rate of thecorrodible surfaces contacted with the mixture is substantially reducedas compared to corrosion of these surfaces when contacted withsulfur-containing material in the absence of the corrosion-reducingliquid. In one embodiment, the corrosion-inhibiting composition does notproduce a stable sulfonated component. In another embodiment, sulfurdoes not accumulate in the turpentine liquid.

In some embodiments, the composition comprises, consists essentially of,or consists of at least from about 0.0001 to 0.002% by volume of thecorrosion-inhibiting composition. In another embodiment, the compositioncomprises, consists essentially of, or consists of at least from about0.0005% by volume of the corrosion-inhibiting composition. In a furtherembodiment, the composition comprises, consists essentially of, orconsists of at least from about 0.001% by volume of thecorrosion-inhibiting composition. In a further embodiment, thecomposition comprises, consists essentially of, or consists of at leastfrom about 0.0015% by volume of the corrosion-inhibiting composition. Ina further embodiment, the composition comprises, consists essentiallyof, or consists of at least from about 0.001% to 0.002% by volume of thecorrosion-inhibiting composition. In another embodiment, the compositioncomprises, consists essentially of, or consists of at least from about0.01% to 10% by volume of the corrosion-inhibiting composition. In afurther embodiment, the composition comprises, consists essentially of,or consists of at least from about 0.1% to 5% by volume of thecorrosion-inhibiting composition. In yet another embodiment, thecomposition comprises, consists essentially of, or consists of at leastfrom about 0.5% to 2% by volume of the corrosion-inhibiting composition.In a further embodiment, the composition comprises, consists essentiallyof, or consists of at least from about 1% by volume of thecorrosion-inhibiting composition.

In a further embodiment, the rate of corrosion is reduced by at leastabout 2-fold as compared to corrosion of the surface when contacted witha sulfur-containing material in an absence of the corrosion-inhibitingcomposition. In this embodiment, the method employs an effective amountof the turpentine liquid acting as the active ingredient to achieve theat least 2-fold level of corrosion reduction.

In another embodiment the rate of corrosion is reduced by at least about3-fold. In a further embodiment, the rate of corrosion is reduced by atleast about 4-fold as compared to corrosion of the surface whencontacted with a sulfur-containing material in an absence of thecorrosion-inhibiting composition.

In certain embodiments, the turpentine liquid is selected from naturalturpentine, synthetic turpentine, mineral turpentine, pine oil,α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, polymersthereof, and mixtures thereof. In certain other embodiments, theturpentine liquid is selected from geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid is selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.

The corrosion-inhibiting composition may be used as a liquidcomposition, or in the vapor phase, nebulized, aerosolized, or appliedas a solid, a thin-film, a condensate, a particulate, or a gel. In oneembodiment, the composition may be deposited as a controlledcondensation of molecular or atomic compounds in liquid or gas phase bya physical or chemical process. The composition may include appropriateadditional ingredients to stabilize the composition in a desired state.For example, the composition can include paints or coating ingredientsand be painted, coated, or sprayed onto a substrate. Any chemicaldeposition technique may be used, for example: Chemical SolutionDeposition (CSD), in the liquid phase by spin-on, aerosol deposition,dipping, electrochemical Deposition (ECD), anodization orelectrophoretic deposition, in the vapor phase by Chemical VaporDeposition (CVD), as well as thermal, plasma, and/or photo deposition.Any physical deposition technique may also be used, for example:Physical Vapor Deposition (PVD), sputtering, evaporation, and/orMolecular Beam Deposition (MBD).

Another embodiment of the invention comprises contacting thesulfur-containing material and/or corrodible surface with a turpentineliquid mixture hereinafter referred to as the blend of turpentineliquids. The blend of turpentine liquids includes α-terpineol,β-terpineol, β-pinene, and p-cymene. In one embodiment, themulti-component turpentine liquid includes at least about 30%α-terpineol, and at least about 15% β-terpineol. In another embodiment,the blend of turpentine liquids includes about 40-60% α-terpineol, about30-40% β-terpineol, about 5-20% β-pinene, and about 0-10% p-cymene. Inanother embodiment, the blend of turpentine liquids includes about 50%α-terpineol, about 35% β-terpineol, about 10% β-pinene, and about 5%p-cymene. In an alternative embodiment, a blend of turpentine liquidsincludes about 40-60% α-terpineol, about 30-40% α-pinene, about 5-20%β-pinene, and about 0-10% p-cymene. In another embodiment, a blend ofturpentine liquids includes about 50% α-terpineol, about 35% α-pinene,about 10% β-pinene, and about 5% p-cymene.

In certain embodiments, the amount of turpentine liquid added to thesulfur-containing material is in a range of about 1 ppm and about 10,000ppm, or in a range of about 10 ppm and about 1,000 ppm. In anotherembodiment the ratio of turpentine liquid to sulfur-containing materialis in a range of about 50 ppm and about 500 ppm. Preferably, about 100ppm of the turpentine liquid is used. In other embodiments, the ratio ofturpentine liquid to sulfur in the sulfur-containing material can be inthe range of about 1:10 to about 10:1, preferably greater than or equalto about 1:1, and yet more preferably greater than or equal to about3:1. In other embodiments the ratio can be greater than or equal toabout 4:1 or 5:1. The amount of sulfur may be measured or estimated andrefers to elemental sulfur and sulfur compounds, including but notlimited to, metal sulfates, sulfides, sulfites, sulfur-containing gases,and sulfur-containing salts and sulfur-containing acids.

In certain embodiments, the corrosion rate of the corrodible surface canbe reduced by at least about 20-40%. In preferred embodiments, thecorrosion rate is reduced by at least about 30%, 50%, or 75%.

In one embodiment of the invention, the corrosion-inhibiting compositioncomprises, consists essentially of, or consists of natural, synthetic ormineral turpentine, which can include α-terpineol, or be α-terpineolitself.

In certain embodiments, the corrosion-inhibiting composition can be usedat a temperature within the range of about 2° C. to about 300° C. Incertain embodiments, the sulfur-containing material and/or corrodiblesurface to be treated is contacted with a turpentine liquid at atemperature of less than about 300° C., less than about 120° C., lessthan 60° C., or at room temperature. In certain other embodiments, thecorrodible material to be protected can be immersed in, coated with,sprayed with, or covered with one or more turpentine liquids.

The present invention avoids the environmental, economic, and practicaldisadvantages that have plagued prior corrosion and scale inhibitor andremoval techniques. To date, chemical and mechanical methods have beenused with varying degrees of success. However, each of these knownsolvent formulations may have certain drawbacks that one or moreembodiments of the current invention overcome. In one embodiment, therenewable and “green” corrosion inhibiting liquids of the presentinvention are naturally derived and free of carcinogenic and pollutantchemicals. Further, the use of the corrosion-inhibiting composition ofthe present invention for protecting corrosion of corrodible surfaces bysulfur-containing materials avoids the economic and environmental costsassociated with other known techniques for corrosion inhibition.

According to an aspect of the present invention, secondary ingredientscan be added to the turpentine liquid. According to a certain aspect ofthe invention, the secondary ingredients can be selected at least one of2,4 diamino-6-mercapto salts, triazoles, e.g., totyl- andbenzo-triazole, dibenzo disulfide, vanadium compounds, ammoniumpolysulfide, oligoquinolinium metal oxide salts, hexylamine, andtreatment compounds disclosed in U.S. Pat. No. 6,328,943, which isincorporated herein by reference, diluents, e.g., lower aliphaticalcohols, alkanes, aromatics, aliphatic amines, aromatic amines, carbonbisulfide, decant oil, light cycle oil and naphtha, and buffers.

As used herein, lower aliphatic alcohols refers to primary, secondaryand tertiary monohydric and polyhydric alcohols of between 2 and 12carbon atoms. As used herein, alkanes refers to straight chain andbranched chain alkanes of between 5 and 22 carbon atoms. As used herein,aromatics refers to monocyclic, heterocyclic and polycyclic compounds.As used herein, aliphatic amines refers to primary, secondary andtertiary amines having alkyl substituents of between 1 and 15 carbonatoms. In certain embodiments, benzene, naphthalene, toluene orcombinations thereof are used. In another embodiment, the loweraliphatic alcohols noted above can be used. In one embodiment thesolvent is selected from ethanol, propanol, isopropanol, butanol,pentane, heptane, hexane, benzene, toluene, xylene, naphthalene,anthracene, tetraline, triethylamine, aniline, carbon bisulfide, andmixtures thereof.

Exemplary Embodiments for Carrying Out the Invention

In one embodiment, the present invention provides a method of treatmentfor inhibiting sulfur-based corrosion or scaling or for removing scalingfrom a surface. The inventive method includes inhibiting corrosioncaused by sulfur-containing materials, reducing corrosion caused bysulfur-containing materials, inhibiting scaling caused bysulfur-containing materials, reducing scaling caused bysulfur-containing materials, and removing scaling caused bysulfur-containing materials. The method includes contactingsulfur-containing materials with a composition comprising, consistingessentially of, or consisting of a turpentine liquid. In a furtherembodiment, the inventive method includes contacting the surface withthe inventive composition. In yet another embodiment, the inventivemethod involves both contacting the sulfur-containing material and thesurface with a composition comprising, consisting essentially of, orconsisting of a turpentine liquid.

The turpentine liquid can comprise, consist essentially of, or consistof natural turpentine, synthetic turpentine, mineral turpentine, pineoil, α-pinene, β-pinene, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.

The corrosion-inhibiting and/or scale-inhibiting composition is said toconsist essentially of the turpentine liquid if the turpentine liquid isthe essential active ingredient for substantially all of the corrosionand/or scaling inhibition and other ingredients in the composition areessentially inactive or non-active in corrosion and/or scalinginhibition. Thus, in certain embodiments, the basic and novelcharacteristics of the present invention include a compositionconsisting essentially of a turpentine liquid that excludes other activecorrosion inhibiting ingredients.

In certain embodiments, the inventive composition is substantially acidfree or the method involves contacting said surface or sulfur-containingmaterial with a substantially acid free turpentine liquid. Asubstantially acid-free composition contains less than about 10% acid.In a preferred embodiment, a substantially acid-free compositioncontains less than about 5% acid. In yet a more preferred embodiment, asubstantially acid-free composition contains less than about 3% acid. Inan even more preferred embodiment, a substantially acid-free compositioncontains less than about 1% acid. By using a substantially acid-freecomposition, the present invention avoids the problems associated withacid-containing compositions that initiate new scaling and corrosionfrom the byproducts generated by acid-sulfur contact.

In another embodiment, the inventive composition is substantiallynon-aqueous or the method involves contacting said surface orsulfur-containing material with a substantially non-aqueous turpentineliquid. In a preferred embodiment the turpentine liquid is non-aqueous.By using a substantially non-aqueous composition, the present inventionavoids the problems associated with aqueous compositions that initiatednew scaling and corrosion from the byproducts generated by water-sulfurcontact.

In yet another embodiment, the invention comprises using a compositionthat consists essentially of a turpentine liquid, i.e, is asubstantially non-aqueous and/or substantially acid-free turpentineliquid. By using a substantially sulfur-free composition, the presentinvention avoids the problems associated sulfur-containing compositionsthat initiate new scaling and corrosion from reactions with sulfurcontained within the existing anti-corrosion and/or anti-scalingcompositions.

In one embodiment, the composition of the present invention issubstantially free of sulfur compounds, acids, or salts. In a furtherembodiment, the invention comprises using a composition that consistsessentially of a sulfur-free turpentine liquid, i.e, is a substantiallynon-aqueous and/or substantially acid-free turpentine liquid, andsubstantially free of sulfur compounds, acids, or salts. Thus, in theseembodiments, the present invention avoids the drawbacks andineffectiveness associated with sulfur-containing, acidic and/or aqueouscompositions of corrosion and/or scaling treatments.

As used herein, the term “non-active” shall mean that the ingredient isnot present in an effective active amount for corrosion and/or scalinginhibition.

In one embodiment, the inventive method substantially reduces thecorrosion rate of a corrodible surface contacted with asulfur-containing material when compared to corrosion of the samesurface when contacted with the same sulfur-containing material in theabsence of the turpentine liquid.

As used herein, the term “substantially reduces” shall mean the rate ofcorrosion is reduced by at least about 2-fold as compared to corrosionof said surface when contacted with said sulfur-containing material inthe absence of contact with the composition. Preferably, the rate ofcorrosion is reduced by at least about 3-fold, and yet more preferably,the rate of corrosion is reduced by at least about 4-fold as compared tocorrosion of said surface when contacted with said sulfur-containingmaterial in the absence of contact with the composition.

In one embodiment, the turpentine liquid comprises α-terpineol,β-terpineol, β-pinene, p-cymene, or a combination thereof. In apreferred embodiment, the turpentine liquid comprises about 40 to 60%α-terpineol, about 30 to 40% β-terpineol, about 5 to 20% β-pinene, andabout 0 to 10% p-cymene. In another preferred embodiment, the turpentineliquid comprises about 40 to 60% α-terpineol or β-terpineol, about 5 to40% α-pinene or β-pinene, and about 0 to 20% p-cymene.

In certain embodiments, the sulfur-containing material that contacts acorrodible surface to be protected is a sulfur-containing liquid, gas,vapor, solid, or a combination thereof. Such sulfur-containing materialsmay contain elemental sulfur, sulfur-containing acids, sulfur-containingsalts, organic sulfur compounds, inorganic sulfur compounds, orcombinations thereof.

In another embodiment of the invention, the inventive method of includesa further step for separating the turpentine liquid from thesulfur-containing material. In a preferred embodiment, the separatedturpentine liquid is recycled.

In one embodiment of the inventive method, the composition is applied asa layer on a corrodible surface. In certain embodiments, the layer isapplied directly on said surface. In other embodiments, the layer isdirectly applied to the corrodible surface and is then covered byanother protective layer. In another embodiment, the composition isapplied as a layer over a protective layer which has been applieddirectly onto the corrodible surface. In one embodiment, the protectivelayer, which is applied over and/or under the layer of the inventivecomposition, is an insulation layer.

In certain embodiments, the invention provides a method of removingscale from a surface in need thereof, e.g., a surface prone to scalingor a surface with scale build-up. The inventive method includes thesteps of mechanically removing existing scale from the surface,contacting the surface with a composition including an effective amountof a scale-removing turpentine liquid. The turpentine liquid includes atleast one of natural turpentine, synthetic turpentine, mineralturpentine, pine oil, α-pinene, β-pinene, α-terpineol, β-terpineol,γ-terpineol, polymers thereof, and mixtures thereof. In certain otherembodiments, the turpentine liquid is selected from geraniol, 3-carene,dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide,terpin hydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, and mixtures thereof. In otherembodiments, the turpentine liquid is selected from anethole, camphene;p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate,ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof. Preferably, the scale-removingturpentine liquid includes α-terpineol, β-terpineol, β-pinene, p-cymene,or combinations thereof. Even more preferably, the turpentine liquidincludes about 40 to 60% α-terpineol, about 30 to 40% β-terpineol, about5 to 20% β-pinene, and about 0 to 10% p-cymene. Yet more preferably, theturpentine liquid includes about 40 to 60% α-terpineol or β-terpineol,about 5 to 40% α-pinene or β-pinene, and about 0 to 20% p-cymene.

The inventive method provides an advantageous technique for inhibitingcorrosion of a corrodible surface that is prone to corrosion caused byits reaction with sulfur-containing materials. The technique includescontacting the sulfur-containing material with a composition containinga turpentine liquid, contacting the corrodible surface with thecomposition, or contacting both the surface and the sulfur-containingmaterial with the inventive composition. Any type of corrosion may beinhibited by the inventive method, including pitting corrosion, generalor uniform corrosion, creep corrosion, stress corrosion, blistering,vapor phase corrosion, crevice corrosion, welding corrosion, andmicrobial corrosion.

Corrodible surfaces that can be treated with the presently claimedmethod include metal surfaces, concrete surfaces, composite surfaces,plastic surfaces, natural polymer surfaces, wood surfaces, and glasssurfaces.

In one embodiment, the inventive method involves contacting the surfaceto be treated prior to and/or during reaction of the surface with asulfur-containing material.

The inventive method also inhibits and/or reduces scale from building upon a surface that is prone to scale buildup. This scale build up can becaused by contact with sulfur-containing material and/or other ionic andmineral scales. The method involves treating the scale-causing materialwith a composition containing a turpentine liquid, contacting thesurface with the composition, or contacting both the material and thesurface with the composition. In one embodiment, the scale can be causedby contact with sulfur or sulfur compounds in any material and the scalecan form as a by product of corrosion or by adhesion of sulfur and otherprecipitates to surfaces prone to scaling. Thus, in certain embodiments,the inventive method can be used to inhibit and/or reduce scalingformation on surfaces before corrosion. The scale causing sulfur may befound in any material including non-hydrocarbon-containing materials,hydrocarbon-containing materials, and mixtures thereof.

The inventive method can also include the step of mechanically removingscale from said surface, before, during or after treatment with theinventive composition. The inventive method involves reducing theadhesion of sulfur to the surface which is prone to scale buildup in theabsence of the inventive composition. Further, the method involvesreducing the agglomeration of sulfur in the sulfur-containing material.

WORKING EXAMPLES Example 1

The effect of corrosion inhibitors on the corrosion rate of API X-65carbon steel in a simulated sulfur-containing environment was tested.The environment was ASTM substitute seawater with 500 ppm Na₂S, pHadjusted to 4.8 using acetic acid. Inhibitor concentrations of 100 ppmwere used in each of the applicable tests. A baseline solution was alsotested. The test temperature was 100° F. on all tests. Two week stirredglass reaction kettle tests were used to determine the general corrosionrate and examine the formation of localized corrosion in a sourenvironment with and without various corrosion inhibitors.

Chemical analysis of the steel test coupons is given in Table 1 (weight%):

C P S Si Mn Cr Mo Al B .060 .008 .005 .300 1.330 .050 .030 .020 .0022 CuNi N Nb Ca Ti V .300 .010 .0093 .048 .0032 .017 .023

The physical properties of the steel test coupons were:

Tensile Strength, KSI: 86.32

Yield Strength, KSI: 76.24

Elongation, % in 2 in.: 37.0

The chemical composition of the substitute seawater is given in Table 2:

Component Weight % NaCl 58.490 MgCl₂•6H₂O 26.460 Na₂SO₄ 9.750 CaCl₂2.765 KCl 1.645 NaHCO₃ 0.477 KBr 0.238 SrCl₂•6H₂O 0.095 H₃BO₃ 0.071 NaF0.007

The corrosion tests were conducted in one-liter glass reaction kettles.The test coupons were mounted using PTFE supports (see FIG. 1A) andcrevice washers (see FIG. 1B). The crevice washers produce crevices onthe coupons that can be statistically analyzed. The test solution (ASTMsubstitute seawater) was deaerated for a minimum of 16 hours with N₂ inthe glass reaction kettle and then heated to 100° F. before beingtransferred. The PTFE mounted samples and the various corrosioninhibitors (where applicable) were placed in the reaction kettle andpurged with N₂ for one hour. Na₂S was allowed to liquefy by mixing itwith deaerated test solution and then injected into the solutiontransfer line prior to the actual transfer of solutions. The testsolution was pushed out of the reaction kettle and into the vesselcontaining the coupons using gas pressure. The vessel was then heated to100° F. N₂ was slowly bubbled through the reaction kettles for theduration of the test to prevent oxygen contamination. The duration ofthe test was 14 days. After testing, the coupons were cleaned accordingto ISO 9226, and the corrosion rates determined. The coupons wereexamined for localized corrosion (pitting and/or crevice corrosion).

Baseline solution results. The test coupons tested with baselinesolution showed crevice and localized corrosion (see FIGS. 2 and 3).

The corrosion rate data for these test coupons are given in Table 3:

Sample 01 02 Initial Weight (g) 16.1143 16.3113 Final Weight (g) 16.106616.3037 Weight Loss (g) 0.0077 0.0076 Surface area (cm²) 27.8435 27.9573Corrosion Rate (mpy) 0.36 0.36 Average Corrosion Rate (mpy) 0.36

Inhibitor results. The test coupons tested with three differentinhibitor compositions (I-III) demonstrated significantly reducedcorrosion rates compared to the baseline samples. Inhibitor I included50% α-terpineol, 30% β-pinene, 10% α-pinene, and 10% para cymene.Inhibitor II included 50% α-terpineol, 10% β-pinene, 10% α-pinene, and30% para cymene. Inhibitor III included 40% α-terpineol, 30% β-pinene,10% α-pinene, and 20% para cymene. Here, the average corrosion rateswere 0.28 (Inhibitor II), 0.24 (Inhibitor I), and 0.09 (Inhibitor III)mpy (see FIGS. 4A-C). The corrosion rates recorded directly coincidewith the amount of crevice attack observed on each test coupon.

Example 2

The effect of corrosion inhibitors on the corrosion rate of AISI 1018carbon steel in a simulated elemental sulfur-containing environment wastested. The environment was distilled water with elemental sulfur addedat 1.6 g/L (0.05 mol/l). About 0.15 mol of each inhibitor was used ineach of the applicable tests (3:1 molar ratio of inhibitor to sulfur). Abaseline solution was also tested. The test temperature was 300° F. onall tests. The corrosion tests were conducted in one-liter, PTFE linedstainless steel autoclaves. No crevice washers were used.

Chemical analysis of the steel test coupons is given in Table 4 (weight%):

C Al Ca Cr Cu Mn Mo Ni P S Si 0.19 .03 .001 .03 .08 .67 .02 .04 .006.001 .02

Baseline solution results. The test coupons tested with baselinesolution showed extensive corrosion showing both edge and pitting attack(see FIG. 5). The corrosion rate data for these baseline test couponsare given in Table 5:

Sample 07 08 Initial Weight (g) 14.4513 14.5189 Final Weight (g) 13.579513.5552 Weight Loss (g) 0.8718 0.9637 Surface area (cm²) 27.8610 27.8823Corrosion Rate (mpy) 40.79 45.05 Average Corrosion Rate (mpy) 42.92

Inhibitor results. The test coupons tested with inhibitor compositionsdemonstrated significantly reduced corrosion rates compared to thebaseline samples. Here, the average corrosion rates were 20.61 forInhibitor I (see FIG. 6) and 12.90 mpy for Inhibitor II (see FIG. 7).

Scanning electron microscope images of the coupon surfaces after testingin each of the 14 day 3:1 inhibitor to sulfur molar ratio environments(see FIG. 8). The baseline coupon had a voluminous corrosion product(see FIG. 8A). The inhibitor I coupon had a relatively smooth corrosionproduct with some areas of heavier deposits (see FIG. 8B). The inhibitorII coupon had a smooth corrosion product with very few areas of heavierdeposits (see FIG. 8C).

Table 6 provides the compositional analysis of corrosion products forthe three test coupons (atomic %):

Sample S Fe Cr Si O Baseline 58.65 41.35 — — — Inhibitor I 46.19 53.560.16 0.08 — Inhibitor II 51.19 47.12 0.09 0.50 1.10

In an accelerated corrosion test, the test duration has a significantinfluence on the absolute corrosion rate. Most general corrosionmechanisms exhibit an asymptotically decreasing corrosion rate withtime. This causes short term tests to artificially appear to have ahigher corrosion rate than long term tests. Thus, a baseline test isperformed for each time period, permitting comparison, regardless of theabsolute corrosion rate.

In these tests, the inhibitors were effective for protecting againstpitting. In the case of pitting, the general corrosion rate is much lesssignificant than the depth of attack. If the depth of attack is large,the pipe may fail, even with a reasonable general corrosion rate. Theinventive corrosion-inhibiting compositions were effective in mitigatingthe depth of attack caused by the elemental sulfur.

Example 3

The effect of corrosion inhibitors on the formation of localizedcorrosion of AISI 1018 carbon steel in a sulfur-containing environmentwas tested. Colloidal sulfur (0.4 g) was used in testing. The sulfur wasmelted to form approximately 3 pieces of sulfur for each coupon. Thethree sulfur pieces were then placed on top of each horizontally mountedsteel coupon. For the inhibited tests, the sulfur pieces were exposed toneat inhibitors for approximately 1 hour. The test environment wasdeaerated substitute seawater, saturated with 86 psig H₂S and 20 psi CO₂for a total pressure of 106 psig prior to heating to 140° F. (60° C.).The tests consisted of a baseline test with unexposed sulfur and twotests with inhibitor exposed sulfur. The corrosion tests were conductedin one-liter, stainless steel autoclaves. The coupon was suspended offthe bottom of the autoclave using PTFE supports. The uninhibited testwas slowly stirred, but there was no stirring in the inhibited tests.The test duration was 6 days. After exposure the coupon was removed fromthe autoclave and photographed. The coupon was cleaned, and thecorrosion rate and localized corrosion determined.

Chemical analysis of the steel test coupons is given in Table 7 (weight%):

C Al Cr Cu Mn Ni P S Si 0.17 .042 .04 .02 .80 .01 .014 .002 .022

Baseline solution results. The test coupons tested with baselinesolution showed pitting in one of the three sulfur piece locations onthe uninhibited coupon (see FIGS. 9A-C). It is likely that the sulfurcame off at the other two locations due to the agitation. The maximumpitting depth was 24 mils, with a close up view of the pitted area shownin FIG. 9D. If the pitting rate during the six day test were constantover a year, the depth of attack would be 1402 mils, or almost 1½inches. This shows the extensive damage that can be done on a metal byfree sulfur. The general corrosion rate over the surface of the couponwas 26 mpy.

Inhibitor results. The test coupons tested with sulfur pieces contactedwith inhibitors demonstrated a lack of pitting corrosion. There weresome markings on the top of the sample where the sulfur had initiallybeen placed. FIGS. 10A-C show the inhibitor I coupon and FIGS. 10D-Fshow the inhibitor II coupon after cleaning. This solution was notstirred, and the spots on the bottom of the coupon are likely due to gasbubbles. The general corrosion rate over the surface of the coupon was11 mpy for the inhibitor I coupon and 19 mpy for the inhibitor IIcoupon. None of the sulfur pieces remained on the coupon surface at theend of the test, even without agitation demonstrating that theinhibitors prevent the adhesion of sulfur to the metal surface.

Example 4

This test was conducted to determine the surface adherence of freesulfur as well as the extent to which the inhibitor causes sulfur toagglomerate. Powdered sulfur (1 g) was added to 100 mL of distilledwater in 6 oz bottles at room temperature (FIG. 11A). The inhibitorswere injected at 1000 ppm and the bottles vigorously shaken 50 times.Photographs were taken before (FIGS. 11A, C, E) and after shaking (FIGS.11B, D, F), and the effect of the inhibitors on the dispersibility ofthe sulfur was recorded (see FIGS. 11C-F).

The adherence of the sulfur to the sides of the glass container wassignificantly reduced in the inhibited tests. This indicates that theinhibitor sequesters the sulfur from the surface of the glass. This isan indicator of reduction in polarity between the free sulfur and glassor silica. Further, the sulfur did not agglomerate in the presence ofthe inhibitors.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the specification and practiceof the invention disclosed herein as well as equivalents thereof. It isintended that the specification and examples be considered as exemplaryonly, with a true scope and spirit of the present invention beingindicated by the following claims and equivalents thereof.

1. A method of treatment for inhibiting sulfur-based corrosion orscaling or for removing scaling from a surface, said method selectedfrom the group consisting of inhibiting corrosion caused bysulfur-containing materials, reducing corrosion caused bysulfur-containing materials, inhibiting scaling caused bysulfur-containing materials, reducing scaling caused bysulfur-containing materials, and removing scaling caused bysulfur-containing materials, comprising contacting saidsulfur-containing material with a composition comprising a turpentineliquid, contacting said surface with said composition, or a combinationthereof.
 2. The method of claim 1, wherein said turpentine liquid isselected from the group consisting of natural turpentine, syntheticturpentine, mineral turpentine, pine oil, α-pinene, β-pinene,α-terpineol, β-terpineol, γ-terpineol, terpene resins, α-terpene,β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.
 3. The method of claim 1, wherein saidturpentine liquid is selected from the group consisting of syntheticturpentine, pine oil, α-terpineol, β-terpineol, γ-terpineol, terpeneresins, α-terpene, β-terpene, γ-terpene, geraniol, 3-carene, dipentene(p-mentha-1,8-diene), nopol, pinane, 2-pinane hydroperoxide, terpinhydrate, 2-pinanol, dihydromycenol, isoborneol, p-menthan-8-ol,α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.
 4. The method of claim 1, wherein saidturpentine liquid is selected from the group consisting of geraniol,3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane, 2-pinanehydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol, isoborneol,p-menthan-8-ol, α-terpinyl acetate, citronellol, p-menthan-8-yl acetate,7-hydroxydihydrocitronellal, menthol, anethole, camphene; p-cymene,anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornyl acetate, ocimene,alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.
 5. The method of claim 1, wherein saidcomposition comprises greater than about 0.0005% of said turpentineliquid.
 6. The method of claim 5, wherein said composition comprisesgreater than about 0.001% of said turpentine liquid.
 7. The method ofclaim 6, wherein said composition comprises about 0.0015% of saidturpentine liquid.
 8. The method of claim 1, wherein said composition isin an amount that corresponds to an amount of at least about 0.001% to0.002% of said sulfur-containing material.
 9. The method of claim 1,wherein the rate of said corrosion is reduced by at least about 2-foldas compared to corrosion of said surface when contacted with saidsulfur-containing material in an absence of said composition.
 10. Themethod of claim 1, wherein the rate of said corrosion is reduced by atleast about 3-fold as compared to corrosion of said surface whencontacted with said sulfur-containing material in an absence of saidcomposition.
 11. The method of claim 1, wherein the rate of saidcorrosion is reduced by at least about 4-fold as compared to corrosionof said surface when contacted with said sulfur-containing material inan absence of said composition.
 12. The method of claim 1, wherein saidturpentine liquid comprises about 40 to 60% α-terpineol, about 30 to 40%β-terpineol, about 5 to 20% β-pinene, and about 5 to 10% p-cymene. 13.The method of claim 1, wherein said turpentine liquid comprises about 40to 60% α-terpineol or β-terpineol, about 5 to 40% α-pinene or β-pinene,and about 5 to 20% p-cymene.
 14. The method of claim 1, wherein saidsulfur-containing material is selected from the group consisting ofsulfur-containing liquids, gases, vapors, solids, and combinationsthereof.
 15. The method of claim 1, wherein said sulfur-containingmaterial contains elemental sulfur, sulfur acids, sulfur salts, organicsulfur compounds, inorganic sulfur compounds, or a combination thereof.16. The method of claim 1, further comprising separating said turpentineliquid from said sulfur-containing material.
 17. The method of claim 16,further comprising recycling said turpentine liquid separated from saidsulfur-containing material.
 18. The method of claim 1, wherein saidcontacting comprises applying said composition as a layer on saidsurface.
 19. The method of claim 18, wherein said layer is applieddirectly on said surface.
 20. The method of claim 19, wherein said layerdirectly applied to said surface is covered by another protective layer.21. The method of claim 1, wherein said composition is applied to saidsurface as a liquid, a solid, a thin film, a condensate, a gas or avapor, aerosolized, a gel, or a combination thereof.
 22. The method ofclaim 1, wherein said composition is applied by chemical vapordeposition, chemical solution deposition, spin-on, aerosol deposition,dipping, anodization, electrophoretic deposition, thermal deposition,photo deposition, plasma deposition, sputtering, evaporation, molecularbeam deposition, physical vapor deposition, or a combination thereof.23. The method of claim 1, wherein said composition is applied bychemical vapor deposition, spin-on, aerosol deposition, anodization,electrophoretic deposition, thermal deposition, photo deposition, plasmadeposition, sputtering, evaporation, molecular beam deposition, physicalvapor deposition, or a combination thereof.
 24. The method of claim 1,wherein said sulfur-containing material is contacted with about 1 ppm to10,000 ppm of said turpentine liquid.
 25. The method of claim 24,wherein said sulfur-containing material is contacted with about 10 ppmto 1,000 ppm of said turpentine liquid.
 26. The method of claim 25,wherein said sulfur-containing material is contacted with about 50 ppmto 500 ppm of said turpentine liquid.
 27. The method of claim 1, whereinthe ratio of said turpentine liquid to said sulfur-containing materialis about 1:10 to 10:1.
 28. The method of claim 1, wherein the ratio ofsaid turpentine liquid to said sulfur-containing material is greaterthan or equal to about 1:1.
 29. The method of claim 28, wherein saidratio is about 3:1 to 5:1.
 30. The method of claim 1, wherein saidsulfur-containing material is a hydrocarbon containing material.
 31. Themethod of claim 1, wherein said sulfur-containing material is anon-hydrocarbon containing material.
 32. The method of claim 1, whereinsaid surface is selected from the group consisting of a metal, acomposite, a concrete, a plastic, a natural polymer, a wood, and a glasssurface.
 33. The method of claim 32, wherein said metal comprises steel,aluminum, and/or copper.
 34. The method of claim 1, wherein said surfaceis a surface prone to corrosion of a pipe, a tank, a boiler, a heater, awire, a semiconductor, a ship, a boat, a shipping container, a hotchamber of a naval vessel, a port structure, an offshore structure, anairplane, a helicopter, a jet exhaust component, a jet engine turbine, aflue stack, an exhaust stack, an electronic component, a casing, afishing tool, or a drill bit.
 35. The method of claim 1, wherein saidcomposition further comprises a 2,4 diamino-6-mercapto salt, a triazole,a vanadium compound, an ammonium polysulfide, an oligoquinolinium metaloxide salt, a hexylamine, a lower aliphatic alcohol, an alkane, anaromatic compound, an aliphatic amine, an aromatic amine, a carbonbisulfide, a decant oil, a light cycle oil, a naphtha compound, abuffer, or a mixture thereof.
 36. The method of claim 1, wherein saidcomposition further comprises benzene, naphthalene, toluene, ethanol,propanol, isopropanol, butanol, pentane, heptane, hexane, benzene,toluene, xylene, naphthalene, anthracene, tetraline, triethylamine,aniline, a solvent, carbon bisulfide, or a mixture thereof.
 37. A methodof inhibiting, reducing, or removing sulfur-based corrosion or scalingfrom a surface, wherein said surface is prone to scaling or said surfaceis prone to corrosion caused by a contact with a sulfur-containingmaterial, comprising contacting said sulfur-containing material with acomposition comprising a turpentine liquid, wherein said turpentineliquid is substantially acid free or substantially non-aqueous, orsubstantially free of sulfur compounds, sulfur acids, and/or sulfursalts,
 38. The method of claim 37, wherein said sulfur-containingmaterial is a hydrocarbon-containing material
 39. The method of claim37, wherein said sulfur-containing material is a non-hydrocarboncontaining material.
 40. The method of claim 37, wherein said turpentineliquid is selected from the group consisting of synthetic turpentine,pine oil, γ-terpineol, terpene resins, α-terpene, β-terpene, γ-terpene,geraniol, 3-carene, dipentene (p-mentha-1,8-diene), nopol, pinane,2-pinane hydroperoxide, terpin hydrate, 2-pinanol, dihydromycenol,isoborneol, p-menthan-8-ol, α-terpinyl acetate, citronellol,p-menthan-8-yl acetate, 7-hydroxydihydrocitronellal, menthol, anethole,camphene; p-cymene, anisaldeyde, 3,7-dimethyl-1,6-octadiene, isobornylacetate, ocimene, alloocimene, alloocimene alcohols,2-methoxy-2,6-dimethyl-7,8-epoxyoctane, camphor, citral,7-methoxydihydro-citronellal, 10-camphorsulphonic acid, cintronellal,menthone, and mixtures thereof.